Substituted quaterrylene tetracarboxylic acid diimides

ABSTRACT

Quaterrylenetetracarboxylic diimides I ##STR1## where R is hydrogen; 
     C 1  -C 30  -alkyl whose carbon chain may be interrupted by one or  e of --O--, --S--, --NR 1  --, --CO-- and/or --SO 2  -- and which may be monosubstituted or polysubstituted by cyano, C 1  -C 6  -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which may contain further heteroatoms and may be aromatic, where 
     R 1  is hydrogen or C 1  -C 6  -alkyl; 
     C 5  -C 8  -cycloalkyl whose carbon skeleton may be interrupted by one or more of --O--, --S-- and/or --NR 1  --; 
     aryl or hetaryl, which may each be monosubstituted or poly-substituted by C 1  -C 18  -alkyl, C 1  -C 6  -alkoxy, cyano, --CONHR 2 , --NHCOR 2  and/or aryl- or hetaryl-azo, which may each be substituted by C 1  -C 10  -alkyl, C 1  -C 6  -alkoxy or cyano, where 
     R 2  is hydrogen; C 1  -C 18  -alkyl; aryl or hetaryl, which may each be substituted by C 1  -C 6  -alkyl, C 1  -C 6  -alkoxy, halogen or cyano; 
     X is halogen; C 1  -C 18  -alkyl; aryloxy, arylthio, hetaryloxy or hetarylthio, which may each be substituted by C 1  -C 4  -alkyl or C 1  -C 4  -alkoxy; 
     n is from 2 to 12, 
     their preparation and use as pigments or fluorescent dyes.

This application is a 371 of PCT/EP96/00118 filed Jan. 12, 1996.

The present invention relates to novel quaterrylenetetracarboxylicdiimides of the general formula I ##STR2## where R is hydrogen;

C₁ -C₃₀ -alkyl whose carbon chain may be interrupted by one or more of--O--, --S--, --NR¹ --, --CO-- and/or --SO₂ -- and which may bemonosubstituted or polysubstituted by cyano, C₁ -C₆ -alkoxy or a 5-, 6-or 7-membered heterocyclic radical which is attached via a nitrogen atomand which may contain further heteroatoms and may be aromatic, where

R¹ is hydrogen or C₁ -C₆ -alkyl;

C₅ -C₈ -cycloalkyl whose carbon skeleton may be interrupted by one ormore of --O--, --S-- and/or --NR¹ --;

aryl or hetaryl, which may each be monosubstituted or poly-substitutedby C₁ -C₁₈ -alkyl, C₁ -C₆ -alkoxy, cyano, --CONHR², --NHCOR² and/oraryl- or hetaryl-azo, which may each be substituted by C₁ -C₁₀ -alkyl,C₁ -C₆ -alkoxy or halogen, where

R₂ is hydrogen; C₁ -C₁₈ -alkyl; aryloxy, arylthio, hetaryloxy orhetarylthio, which may each be substituted by C₁ -C₄ -alkyl or C₁ -C₄-alkoxy;

X is halogen; C₁ -C₁₈ -alkyl; aryloxy, arylthio, hetaryloxy orhetarylthio, which may each be substituted by C₁ -C₄ -alkyl or C₁ -C₄-alkoxy;

n is from 2 to 12.

The invention also relates to the preparation of thesequaterrylenetetracarboxylic diimides and to their use as fluorescentdyes or pigments.

Lastly the invention relates to novel 9-haloperylene-3,4-dicarbimides ofthe general formula III ##STR3## where R and X are each as definedabove, Hal is halogen and q is from 2 to 4, as intermediates for thequaterrylenetetracarboxylic diimides I.

EP-A-596 292 describes with reference toN,N'-didodecylquaterrylene-3,4:13,14-tetracarboxylic diimides thepreparation of unsubstituted quaterrylenetetracarboxylic diimides(formula I: n=0; R=n-C₁₂ H₂₅) and their suitability for use asfluorescent dyes and pigments.

Starting from N-dodecylperylene-3,4,9,10-tetracarboxylic 3,4-imide9,10-anhydride, decarboxylation in potassium hydroxide solution undersuperatmospheric pressure and at elevated temperature givesN-dodecylperylene-3,4-dicarbimide, which is brominated toN-dodecyl-9-bromoperylene-3,4-dicarbimide. This is converted byelimination of bromine in the presence of an inert diluent and of anorganometallic catalyst to the corresponding biperylene derivative,where it is finally converted by heating in an alkali medium in thepresence of an oxidizing agent into the abovementioned quaterrylenederivative.

However, EP-A-596 292 does not disclose any way of preparing substitutedquaterrylenetetracarboxylic diimides I (hereinafter shortened to"quaterrylimides") which, however, are of special interest, sincespecific substitution makes it possible for the application properties(eg. solubility, hydrophilicity, lipophilicity, absorption and emissioncharacteristics) to be predetermined and varied.

It is an object of the present invention to provide novel, substitutedquaterrylimides which shall have advantageous application properties(including in the case of fluorescent dyes for example good solubilityin the application media) and hence to provide means for optimumadaptation to the particular intended use.

We have found that this object is achieved by the quaterrylimides of theabove-defined formula I.

Preferred quaterrylimides I are revealed in the subclaims.

We have also found various processes for preparing the quaterrylimidesI, which are likewise revealed in the claims.

Finally, the present invention provides for the use of thequaterrylimides I as pigments or fluorescent dyes.

Last but not least, the 9-haloperylene-3,4-dicarbimides of theabove-defined formula III have been found to be useful as intermediatesfor the preparation of the quaterrylimides I.

Any alkyl appearing in the formulae I and Ia may be straight-chain orbranched. Substituted aryl may generally include up to 3, preferably 1or 2, of the substituents mentioned.

Specific examples of suitable radicals R¹ and X (and of theirsubstituents) are:

methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl,2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl,nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl,isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,nonadecyl and eicosyl (the above designations isooctyl, isononyl,isodecyl and isotridecyl are trivial names derived from the oxo processalcohols--cf. Ullmann's Encyklopadie der technischen Chemie, 4thedition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436);

2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl,2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl,4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl,4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl,3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and3,6,9,12-tetraoxatetradecyl;

2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl,2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2-and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2-and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl,4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-dithianonyl, 4,7-dithiaoctyl,4,7-dithianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl,3,6,9-trithiadecyl, 3,6,9-trithiaundecyl, 3,6,9-trithiadodecyl,3,6,9,12-tetrathiatridecyl and 3,6,9,12-tetrathiatetradecyl;

2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl,6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl,3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl,3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl,3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyland 3,6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl;

propan-2-on-1-yl, butan-3-on-1-yl, butan-3-on-2-yl and2-ethylpentan-3-on-1-yl;

2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl,2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2- and3-ethylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and4-propylsulfonylbutyl and 4-butylsulfonylbutyl;

carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,5-carboxypentyl, 6-carboxyhexyl, 8-carboxyoctyl, 10-carboxydecyl,12-carboxydodecyl and 14-carboxytetradecyl;

sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl,6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and14-sulfotetradecyl;

2-hydroxyethyl, 2-hydroxypropyl, 1-hydroxyprop-2-yl, 2- and4-hydroxybutyl, 1-hydroxybut-2-yl and 8-hydroxy-4-oxaoctyl,2-cyanoethyl, 3-cyanopropyl, 2-methyl-3-ethyl-3-cyanopropyl,7-cyano-7-ethylheptyl and 4-methyl-7-methyl-7-cyanoheptyl;

methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy,tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxy and hexoxy;

carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl,butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl,heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl,decylaminocarbonyl and phenylaminocarbonyl;

formylamino, acetylamino, propionylamino and benzoylamino; chlorine,bromine and iodine;

phenylazo, 2-naphthylazo, 2-pyridylazo and 2-pyrimidylazo;

cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-dioxanyl,4-morpholinyl, 2- and 3-tetrahydrofuryl, 1-, 2- and 3-pyrrolidinyl and1-, 2-, 3- and 4-piperidyl;

phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, 4- and5-pyrimidyl, 3-, 4- and 5-pyrazolyl, 2-, 4- and 5-imidazolyl, 2-, 4- and5-thiazolyl, 3-(1,2,4-triazyl), 2-(1,3,5-triazyl), 6-quinaldyl, 3-, 5-,6- and 8-quinolinyl, 2-benzoxazolyl, 2-benzothiazolyl,5-benzothiadiazolyl, 2- and 5-benzimidazolyl and 1- and 5-isoquinolyl;

2-, 3- and 4-methylphenyl, 2,4-, 3,5- and 2,6-dimethylphenyl,2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 3,5- and2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl,2,4-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and4-isopropylphenyl, 2,4-, 3,5- and 2,6-diisopropylphenyl,2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 3,5- and2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl,2,4-, 3,5 and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and4-sec-butylphenyl, 2,4-, 3,5- and 2,6-di-sec-butylphenyl and2,4,6-tri-sec-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 3,5- and2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl,2,4-, 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and4-propoxyphenyl, 2,4-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and4-isopropoxyphenyl, 2,4- and 2,6-diisopropoxyphenyl and 2-, 3- and4-butoxyphenyl; 2-, 3- and 4-chlorophenyl and 2,4-, 3,5- and2,6-dichlorophenyl; 2-, 3- and 4-hydroxyphenyl and 2,4-, 3,5- and2,6-dichlorophenyl; 2-, 3- and 4-hydroxyphenyl and 2,4-, 3,5- and2,6-dihydroxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxyphenyl;3- and 4-carboxyamidophenyl, 3- and 4-N-methylcarboxamidophenyl and 3-and 4-N-ethylcarboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and4-propionylaminophenyl and 3- and 4-butyrylaminophenyl; 3- and4-N-phenylaminophenyl, 3- and 4-N-(o-tolyl)aminophenyl, 3- and4-N-(m-tolyl)aminophenyl and 3- and 4-(p-tolyl)aminophenyl; 3- and4-(2-pyridyl)aminophenyl, 3- and 4-(3-pyridyl)aminophenyl, 3- and4-(4-pyridyl)aminophenyl, 3- and 4-(2-pyrimidyl)aminophenyl and4-(4-pyrimidyl)aminophenyl;

4-phenylazophenyl, 4-(1-naphthylazo)phenyl, 4-(2-naphthylazo)phenyl,4-(4-naphthylazo)phenyl, 4-(2-pyridylazo)phenyl, 4-(3-pyridylazo)phenyl,4-(4-pyridylazo)phenyl, 4-(2-pyrimidylazo)phenyl,4-(4-pyrimidylazo)phenyl and 4-(5-pyrimidylazo)phenyl;

phenoxy, phenylthio, 2-naphthoxy, 2-naphthylthio, 2-, 3- and4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyrimidyloxy and2-, 4- and 5-pyrimidylthio.

In the novel processes for preparing the ring-substitutedquaterrylimides I, the starting material is in each case aperylene-3,4-dicarbimide II (hereinafter shortened to "perylimide").Depending on the substitution pattern the quaterrylimides I are to have,the starting material is suitably a perylene-3,4-dicarbimide II which iseither unsubstituted or already substituted on the perylene nucleus.

Quaterrylimides of the formula Ia ##STR4## which carry 4 or 8 of thesubstituents X, in positions 1,7,10,16 and 1,7,11,17 or1,6,7,10,11,16,17,20, are advantageously obtained starting from asubstituted perylimide of the formula IIa ##STR5## which already carry 2or 4 of these substituents X, in position 1,7 or 1,6,7,12.

Quaterrylimides of the formula Ib ##STR6## which contain 4 or 8 halogenatoms (preferably chlorine or bromine), in positions 1,6,11,16 or1,6,7,10,11,16,17,20, are obtained according to the invention byselective halogenation of the unsubstituted perylimides of the formulaIIb ##STR7## The number of 8 substituents is achieved in particular inthe case of chlorinated products, which may of course also contain just4 chlorine atoms, while bromination generally brings about a substituentnumber of 4, in each case (especially in the case of the bromination)selectively in the positions mentioned.

Quaterrylimides of the formula Ic ##STR8## which are substituted by 4 or8 substituents Z (aryloxy, arylthio, hetaryloxy or hetarylthio, whichmay each be substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, preferablyphenoxy or pyrimidyloxy), in the positions 1,6,11,16 or1,6,7,10,11,16,17,20 mentioned for the quaterrylimides Ib, are likewisepreparable according to the invention from the unsubstitutedperylene-3,4-dicarbimides IIb by first halogenating the perylimides IIband then subjecting them to a nucleophilic substitution (replacement ofthe halogen atom by the radicals Z).

Quaterrylimides of the formula Id ##STR9## which carry 2, 4, 6, 8 or 12substituents Y (halogen or radicals Z as mentioned to give thequaterrylimides of the formula Ic), preferably in the positions 1,6;1,7,8,18; 1,7,9,11,17,19; 1,6,7,10,11,16,17,20 or1,6,7,8,9,10,11,16,17,18,19,20, can be obtained by halogenation (withnucleophilic replacement) of the unsubstituted quaterrylimides Id' (n=0)which like the substituted quaterrylimides Ia-Ic of the invention arelikewise obtainable from appropriate perylimides II by conversionthereof into 9-haloperylimides (in particular 9-bromoperylimides) III,coupling of two 9-haloperylimides to corresponding biperylenes IV andoxidation thereof to the quaterrylimides I.

The perylene-3,4-dicarbimides II used as starting materials in thepreparation processes of the present invention are described in GermanPatent Application 195 01 737.4 and can with advantage be prepared, andif desired purified, by the processes likewise presented therein.

According to that reference, the perylimides II are prepared by reactingthe appropriately substituted perylene-3,4,9,10-tetracarboxylic acids oranhydrides, especially the dianhydrides, with the desired primary amines(RNH₂).

The perylene-3,4,9,10-tetracarboxylic acids and anhydrides can in turnbe obtained by halogenation and if desired subsequent replacement of thehalogen atoms by aryloxy, arylthio, hetaryloxy, hetarylthio or alkylradicals.

The particularly interesting, 1,7-disubstitutedperylene-3,4,9,10-tetracarboxylic acids and anhydrides are, as describedin German Patent applications 195 47 209.8 and 195 47 210.1, obtainableby a multistage process starting from1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid or dianhydrideprepared by selective bromination of perylene-3,4,9,10-tetracarboxylicacid or dianhydride in 100% strength by weight sulfuric acid at from 80to 90° C. These are reacted in the presence of a polar aprotic solventsuch as N-methylpyrrolidone and optionally of an imidation catalyst, forexample of an organic or inorganic acid or of a transition metal salt,with a primary amine to form the corresponding1,7-dibromoperylene-3,4,9,10-tetracarboxylic diimide, which is thenreacted either in the presence of an inert aprotic solvent such asN-methylpyrrolidone or of a nonnucleophilic or only weakly nucleophilicbase, for example sodium carbonate or potassium carbonate, with anaromatic alcohol or thioalcohol or else in the presence of an aproticsolvent such as tetrahydrofuran, of a palladium complex as catalyst andof a copper salt as cocatalyst and of a base, for example piperidine,with a 1-alkyne. In the last case, 1,7-disubstitutedperylene-3,4,9,10-tetracarboxylic diimides are obtained which containunsaturated bonds in the substituent R² which are reducible bysubsequent stirring in a hydrogen atmosphere or by catalytic reductionwith hydrogen. In a last reaction step, the either 1,7-diaroxy-,-diarlthio- or -dialkyl-substituted perylene-3,4,9,10-tetracarboxylicdiimide is then saponified in the presence of a polar protic solventsuch as isopropanol and of a base, for example sodium hydroxide orpotassium hydroxide, to the 1,7-disubtitutedperylene-3,4,9,10-tetracarboxylic acid or dianhydride.

The reaction of the perylene-3,4,9,10-tetracarboxylic acids oranhydrides with the primary amines RNH₂ is carried out by the processdescribed in German Patent Application 195 01 737.4 in the presence of atertiary nitrogen-base compound as solvent and of a transition metal ortransition metal salt as catalyst.

Examples of suitable nitrogen bases mentioned are cyclic imides such asN-methylpyrrolidone, tertiary aliphatic amines NR³ whose alkyl radicalsR have from 4 to 8 carbon atoms, such as trihexylamine, and inparticular aromatic heterocycles such as quinaldine, isoquinoline and inparticular quinoline.

The amount of solvent will usually range from 2 to 20 kg, preferablyfrom 6 to 12 kg, per kg of perylene-3,4,9,10-tetracarboxylicdianhydride.

The catalysts used are in particular the transition metals iron andespecially zinc and copper and also in particular their inorganic andorganic salts, preferably copper(I) oxide, copper(II) oxide, copper(I)chloride, copper(II) acetate, zinc acetate and zinc propionate.

Typically from 5 to 80% by weight of catalyst are used, based on theperylene-3,4,9,10-tetracarboxylic dianhydride. Preferred amounts rangefrom 10 to 25% by weight in the case of the copper compounds and from 40to 60% by weight in the case of the zinc salts, likewise based on theanhydride.

Suitable primary amines for this process include all primary amineswhich are stable at the reaction temperature, preferably those whoseboiling point at the reaction pressure is above the reactiontemperature.

The reaction temperature is generally from 120 to 250° C., in particularfrom 170 to 235 ° C., and it is said to be advisable to work under aprotective gas (eg. nitrogen) not only at atmospheric pressure but alsoat a superatmospheric pressure of customarily up to 10 bar.

The molar ratio used there between the starting compounds amine andanhydride is generally from 0.8:1 to 6:1. For the atmospheric reactionit is preferably from 0.8:1 to 1.2:1, while for the superatmosphericreaction it is in particular from 2:1 to 4:1.

If the (crude) products obtained by this process do not meet the desiredpurity requirements for the present reaction (the products obtainedgenerally having purities ≧80%), they can be additionally subjected tothe purification process likewise described.

In the purification process of the reference, the crudeperylene-3,4-dicarbimide products are initially heated for about 10-60minutes in usually from 3 to 10, preferably from 5.5 to 6.5, times theweight of N-methylpyrrolidone (NMP in short) to convert them into NMPadducts.

Suitable temperatures range in general from 140 to 200° C., preferablyfrom 160 to 180° C.

If the imide was already prepared in NMP as solvent, this step can bedispensed with, of course.

The isolated NMP adducts are subsequently subjected to alkalinepurification treatment in the presence of an organic diluent at about50-150° C., preferably 60-120° C. If desired, the alkaline treatment canbe followed by an acid aftertreatment.

Suitable diluents include not only inert aromatic solvents such astoluene and xylene but also, with preference, alcohols which can bemonohydric or polyhydric, for example aromatic alcohols such as phenoland benzyl alcohol and aliphatic alcohols, not only glycols and glycolethers, such as ethylene glycol, propylene glycol and butylglycol butalso, in particular, C₂ -C₆ -alcohols such as ethanol, propanol,butanol, pentanol and hexanol, which may each also be branched, such as,preferably, isopropanol.

In general, the diluent is used in an amount of from 40 to 200 kg, inparticular from 80 to 120 kg, per kg of NMP adduct.

Suitable bases include not only sterically hindered nitrogen bases, suchas diazabicycloundecene and diazabicyclo[2.2.2]octane, but especiallyalkali metal hydroxides, such as sodium hydroxide and in particularpotassium hydroxide, which are advantageously used mixed with water, andalkali metal salts of secondary and tertiary aliphatic (preferably C₃-C₆)alcohols, such as sodium tert-butoxide and in particular potassiumtert-butoxide.

It is customary to use from 2 to 15 kg of base per kg of NMP adduct,preferably from 5 to 7 kg, in particular about 6 kg, of dry alkali metalhydroxide or from 0.5 to 1.5 kg, in particular from 0.7 to 1 kg, ofalkoxide or nitrogen base.

If desired, it is possible to follow this up with an additional acidtreatment by suspending the undried filter cake in a dilute inorganicacid, for example 4-6% strength by weight hydrochloric acid (about 4-6kg of acid per kg of filter cake), and the purified imide II can then beisolated in a conventional manner.

In all versions of the preparation according to the present invention,the first step a) is to halogenate the starting perylimide II. Dependingon the quaterrylimides I desired, either only the 9-position of theperylimide is halogenated (preferably brominated) (in cases Ia and Id)or, in addition to the 9-position, 2 or 4 further positions (1- and 6-position or 1-, 6-, 7- and 10-position; syn-halogenation) arehalogenated (in cases Ib and Ic), to obtain the halogenated perylimidesof the formulae IIIa, IIIb and IIId.

What is particularly important is that the substituents R and X are notattacked by halogen.

The halogenation a) according to the present invention is always carriedout in the presence of an inert diluent.

Suitable diluents include not only halogenated aromatics such aschlorobenzene, dichlorobenzene and trichlorobenzene but also, forexample, halohydrocarbons, especially methanes and ethanes, such astribromomethane, tetrachloromethane, tetrabromomethane, 1,2-dichlor-,1,1-dibromo-, 1,2-dibromo-, 1,1,1-trichloro-, 1,1,2-trichloro-,1,1,1-tribromo-, 1,1,2-tribromo-, 1,1,1,2-tetrachloro-,1,1,2,2-tetrachloro-, 1,1,1,2-tetrabromo- and 1,1,2,2-tetrabromo-ethaneand especially dichloromethane (methylene chloride) and trichloromethane(chloroform).

The amount of solvent is not critical per se. The amount will generallyrange from 30 to 200 kg, preferably from 100 to 150 kg, of solvent perkg of perylimide II.

The reaction temperatures generally range from 40 to 140° C. (inparticular up to 90° C.). Depending on the desired degree ofsubstitution, it is advantageous to choose lower or higher temperaturesfrom the range mentioned.

If only the 9-position of the perylimide is to be halogenated,temperatures from 40 to 50° C. are preferable, and the use of methylenechloride as solvent is advisable.

If further positions of the perylene structure are to be halogenated,temperatures from 60 to 90° C. are preferred. The trihalogenation ispreferably carried out at from 60 to 70° C. and the pentachlorination ingeneral at about 75° C., in which case chloroform and1,1,2,2-tetrachloromethane (or else chlorobenzene), respectively, makeparticularly suitable solvents.

The particular advantage here is the selective halogenation, especiallybromination, of the abovementioned positions.

The molar ratio of halogen to perylimide II is usually from 10:1 to100:1, preferably from 40:1 to 60:1 for a bromination and from 10:1 to40:1 for a chlorination.

The halogenation a) can be carried out not only at atmospheric pressurebut also at a superatmospheric pressure up to about 10 bar, and isgenerally complete after 2-10 h, especially 5-7 h. The reaction times doof course also depend on the desired degree of halogenation, andlikewise increase with increasing halogen content.

Step a) is conveniently carried out as follows:

A solution of the perylimide II in the inert solvent is admixed withhalogen, if desired under superatmospheric pressure, and heated to thereaction temperature with vigorous stirring. After a reaction time of2-10 h, cooling and, if applicable, decompression, the reaction mixtureis precipitated in water, the excess halogen is removed, for example byadmixing with an alkaline sulfite solution, the phase containing thehalogenation product is separated off, and the solvent is removed.

The resulting haloperylimides of the formula III ##STR10## where Hal ischlorine or bromine and m is from 0 to 4 (of the correspondinghaloperylimides IIIa-IIId), can be used directly, without furtherpurification, for the next reaction step.

This step (b) comprises in the cases of the quaterrylimides Ia, Ib andId coupling in each case two of the corresponding haloperylimidemolecules III to form a biperylene derivative molecule of the formula IV##STR11## where r is from 0 to 8 (or to the corresponding biperylenederivative molecule IVa, IVb or IVd).

The quaterrylimides Ic first require intermediate step a') whichcomprises replacing the halogen atoms present in the haloperylimidemolecule IIIb, except for the halogen atom in the 9-position, byreaction with a nucleophile of the formula

    Z--K

where Z is aryloxy, arylthio, hetaryloxy or hetarylthio, which may eachbe substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, and K is an alkalimetal cation or hydrogen, in the presence of a tertiary nitrogen base assolvent and optionally of an inorganic base for radicals Z, to obtainhaloperylimides IIIc which are subsequently likewise coupled.

Suitable tertiary nitrogen base solvents include for example aromaticheterocycles, such as quinoline, isoquinoline and quinaldine, and inparticular cyclic imides, especially N-methylpyrrolidone.

The amount of solvent is not critical per se, and is generally from 10to 100 kg, preferably from 20 to 40 kg, per kg of IIIb.

Suitable inorganic bases include for example alkali metal carbonates andhydroxides, in particular potassium carbonate, sodium carbonate,potassium hydroxide and sodium hydroxide, which are preferably used insolid form.

The use of free alcohols or thiols Z--H as nucleophiles generallynecessitates from 10 to 100 times, preferably from 15 to 25 times, themolar amount of inorganic base, based on IIIb. If the alkali metalalkoxides or thiolates are used directly, the addition of inorganic basecan be dispensed with.

It is advisable to use one mole of nucleophile per mole of halogen atomto be replaced. It is of special importance that the halogen atom in the9-position of the perylimide is not substituted, which was not to beexpected.

The reaction temperature in the substitution step a') is generally from90 to 160° C., preferably from 100 to 130° C.

A protective gas can be used, for example nitrogen.

Common reaction times are about 2-10 h, in particular 5-7 h.

If desired, the process can be conducted in a cyclic fashion whereby thedehalogenated substitution product formed as a by-product in step a') isrehalogenated (preferably rebrominated) by step a) and then coupled bystep b).

Step a') is conveniently carried out as follows:

Haloperylimide IIIb, nucleophile and, if used, solid organic base areinitially charged in the solvent and heated, if desired under aprotective gas, to the reaction temperature for about 2-10 h. Aftercooling, the reaction mixture is added with stirring to a diluteinorganic acid, for example dilute hydrochloric acid, and the resultingprecipitate is filtered off, subsequently washed with water, dried and,if necessary, chromatographed over silica gel with aromatic solventssuch as toluene or halogenated hydrocarbons such as chloroform.

The resulting haloperylimide IIIc can be used in the same way as theother haloperylimides IIIa, IIIb and IIId directly for the coupling stepb) to form the biperylene derivatives IV.

The coupling step b) can be carried out analogously to EP-A-596 292 inthe presence of an organic metal complex as catalyst, additional freeligand molecules and an inert diluent.

Suitable inert diluents include for example in particular aliphaticcarboximides, preferably N,N-dimethylformamide andN,N-dimethylacetamide, aliphatic and cycloaliphatic ethers, such asdimethyl ether, 1,2-dimethoxyethane and tetrahydrofuran, and aromatics,such as benzene, toluene and xylene.

The amount of diluent is not critical per se, and ranges in general from20 to 100 kg, preferably from 25 to 45 kg, per kg of haloperylimide III.

The organic metal complexes used as catalysts, as well as palladiumcomplexes such as tetrakis(triphenylphosphine)palladium, include inparticular nickel complexes, for examplebis(triphenylphosphine)nickel(II) chloride,tetrakis(triphenylphosphine)nickel,[1,2-bis(diphenylphosphino)ethane]nickel(II)chloride and preferablybis(1,5-cyclooctadiene)nickel.

The catalysts can also be formed in situ by addition of metal salts orcompounds, free ligands, such as cyclooctadiene, bipyridyl,triphenylphosphine, trifluorophosphine, η-, δ- and π-bonded olefins,cycloolefins, aromatics and antiaromatics, carbonyls, hydrogen andhalogen and also mixtures thereof, and, if necessary, oxidizing orreducing agents.

In general, from 40 to 150 mol %, preferably from 50 to 100 mol %, oforganic metal complex are used, based on III.

In general, it is always advisable to ensure the simultaneous presenceof free ligand molecules, in particular mixtures of cyclooctadiene andbipyridyl in a molar ratio of from 1:1 to 8:1. Suitable amounts rangecustomarily from 80 to 900 mol %, preferably from 80 to 200 mol %, basedon III.

The coupling step b) is advantageously carried out at a temperature offrom 40 to 80° C., preferably from 60 to 65° C., and it may also becarried out under protective gas (eg. argon).

The coupling reaction is generally complete after 36-48 h.

Step b) is conveniently carried out as follows:

Haloperylimide III, organometallic catalyst and free ligand moleculesare initially charged in the inert diluent and heated, optionally undera protective gas, to the reaction temperature for about 36-48 h. Aftercooling, the reaction mixture is added to water, which may containmethanol, a dilute inorganic acid, for example dilute hydrochloric acid,is added, and the resulting precipitate is filtered off, subsequentlywashed with water, dried and, if necessary, chromatographed over silicagel with aromatic solvents such as toluene or xylene.

The resulting biperylene derivatives IV are then converted in step c),analogously to EP-A-596 292, into the quaterrylimides I by heating inthe presence of an oxidizing agent and of an alkaline reaction medium.

Suitable oxidizing agents include for example aluminum chloride,iron(III) chloride, manganese dioxide, palladium(II) acetate, vanadiumoxytrichloride, copper(II) chloride, sodium formaldehydesulfoxylate andin particular glucose.

In general, from 10 to 50 times, preferably 20 to 35 times, the molaramount of the preferred oxidizing agent glucose is used, based on IV.

The alkaline reaction medium used is conveniently a mixture of an alkalimetal hydroxide, especially sodium hydroxide or potassium hydroxide, aC₁ -C₄ -alkanol, such as methanol, ethanol, propanol, isopropanol,butanol, isobutanol or sec-butanol.

The amount used per kg of IV is customarily from 60 to 250 kg,preferably from 100 to 160 kg, of alkali metal hydroxide and from 40 to200 kg, preferably from 70 to 140 kg, of alkanol.

The oxidation c) is advantageously carried out at a temperature of from60 to 180° C., in particular at from 100 to 130° C., and it is alsopossible to use a protective gas, for example argon.

The oxidation is generally complete after 1-4 h, especially 1-2.5 h.

Step c) is conveniently carried out as follows:

Biperylene derivative IV, alkali metal hydroxide, alkanol and oxidizingagent are initially charged and heated, optionally under a protectivegas, to the reaction temperature for 1-2.5 h. After cooling, thereaction mixture is acidified with aqueous mineral acid, for examplehydrochloric acid, and the resulting precipitate is filtered,subsequently washed with water, dried and extracted with inert solvents,such as chloroform, diethyl ether, methyl tert-butyl ether or toluene,to remove any by-products present.

The process leading to the quaterrylimides Id produces in step c) theunsubstituted quaterrylimides Id', which are halogenated subsequently(step d)) and, if desired, can be subjected to a replacement of thehalogen atoms by nucleophilic radicals Z (step e)).

The halogenation step d) can be carried out analogously to thehalogenation step a), but in 1.5-2 times the amount of solvent and ineach case with twice the reaction time.

The decisive requirement is that the halogenation of the quaterrylenemolecule Id' produces the anti-halogenation product (eg.1,7,9,11,17,19-hexabromoquaterrylimide), in contradistinction to stepa).

As in step a), the degree of halogenation here too increases withincreasing temperature and increasing reaction time.

Replacement step e) can likewise be carried out analogously to thecorresponding step a'), but here too from 1.5 to 2 times the amount ofsolvent should be used and the reaction time should be doubled.

The quaterrylimides I of the present invention are advantageously usefulas pigments or fluorescent dyes. They can be used in particular forcoloring macromolecular organic materials or else organic/inorganiccomposites.

Suitable pigments are in particular quaterrylimides of the formula Iwhere R is C₈ -C₂₀ -alkyl, phenyl, pyridyl or pyrimidyl, which may eachbe monosubstituted or polysubstituted by C₁ -C₄ -alkyl ormonosubstituted by phenylazo or naphthylazo, X is halogen and n from 2to 8.

Suitable fluorescent dyes in particular are quaterrylimides of theformula I where R is C₅ -C₈ -cycloalkyl or phenyl, pyridyl or pyrimidyl,which each are monosubstituted or polysubstituted by C₁ -C₄ -alkoxy,--CONHR² or --NHCOR² (R² : C₁ -C₄ -alkyl or phenyl which may besubstituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy), X is phenoxy,phenylthio, pyrimidyloxy or pyrimidylthio which may be substituted by C₁-C₄ -alkyl, and n is from 2 to 8.

EXAMPLES

A1) Preparation of novel 1,6,9-tribromoperylene-3,4-dicarbimides of theformula IIIa' ##STR12##

Example 1a

A solution of 12 g (25 mmol) ofN-(2,6-diisopropylphenyl)perylene-3,4-dicarbimide in 1.5 l of chloroformwas admixed with 75 ml (1.46 mol) of bromine, heated with vigorousstirring to the refluxing temperature (about 61° C.) and held at thattemperature for 6 h.

After cooling down to room temperature, the reaction mixture was addedwith stirring to a solution of 15 g of potassium hydroxide and 10 g ofsodium sulfite in 2 l of water and admixed a little at a time with 6 gof potassium hydroxide and 4 g of sodium sulfite until the excessbromine had all been removed (evident from the change of color from darkreddish brown to bright orange). The organic phase was separated off andthe brominated perylimide IIIa' was isolated by removing all the solventby stripping.

This gave 19.5 g ofN-(2,6-diisopropylphenyl)-1,6,9-tribromoperylene-3,4-dicarbimide in theform of an orange solid having a purity of 84% and a melting point >300°C., which corresponds to a yield of 91%.

Examples 2a to 5a

The method of Example 1a was also employed to prepare thebromoperylimides IIIa' mentioned in Table A by reaction of thecorresponding unhalogenated perylimides with bromine. Example 1a is alsolisted for clarity.

                  TABLE A                                                         ______________________________________                                                           Yield            mp.                                       Ex.    R           in %      Color  [° C.]                             ______________________________________                                        1a     2,6-Diiso-  91        orange >300                                             propylphenyl                                                           2a     Dodecyl     92        red    >300                                      3a     4-tert-Butyl-                                                                             100       bright red                                                                           >300                                             phenyl                                                                 4a     4-Phenylazo-                                                                              95        dark red                                                                             >350                                             phenyl                                                                 5a     2-Methylphenyl                                                                            98        bright red                                                                           >300                                      ______________________________________                                    

A2) Preparation of novel 1,7,9-tribromoperylene-3,4-dicarbimides of theformula IIIa" ##STR13##

Example 6a

R=2,6-diisopropylphenyl

15.9 g (25 mmol) ofN-(2,6-diisopropylphenyl)-1,7-dibromoperylene-3,4-dicarbimide werereacted with 75 ml (1.46 mol) of bromine as described in Example 1a, butat 40° C. in 1.2 l of methylene chloride as solvent.

The 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydride used asprecursor for the preparation of the 1,7-dibrominated perylimide wasobtained by selective bromination of perylene-3,4,9,10-tetracarboxylicdianhydride.

A mixture of 292.5 g (0.75 mol) of perylene-3,4,9,10-tetracarboxylicdianhydride (purity>98%) and 4420 g of 100% strength by weight sulfuricacid was heated to 85° C. after stirring for 12 hours and the subsequentaddition of 7 g of iodine. 262.5 g (1.64 mol) of bromine were then addeddropwise over 8 h. After cooling down to room temperature and displacingthe excess bromine by means of nitrogen, the sulfuric acid concentrationof the reaction mixture was reduced to 86% by weight by adding a totalof 670 g of water a little at a time over 1 h. After cooling thereaction mixture, which had heated up to 85° C., to room temperature,the precipitated product was filtered off on a G4 glass frit, washedwith 3 kg of 86% by weight sulfuric acid, then resuspended in 5 l ofwater, filtered again, washed neutral and dried under reduced pressureat 120° C.

The reaction of Example 6a gave 18.5 g ofN-(2,6-diisopropylphenyl)-1,7,9-tribromoperylene-3,4-dicarbimide as areddish orange solid having a purity of 95% and a melting point >300°C., which corresponds to a yield of 98%.

B1) Preparation of novel 1,6-diaryloxy-9-bromoperylene-3,4-dicarbimidesof the formula IIIb' ##STR14##

Example 1b

A mixture of 16 g (22 mmol) of the tribromoperylimide of Example 1a, 6.6g (44 mmol) of 4-tert-butylphenol and 6.9 g (50 mmol) of potassiumcarbonate in 500 ml of N-methylpyrrolidone was heated at 120° C. for 6h.

After cooling down to room temperature, the reaction mixture was addedwith stirring into 2 l of 5:1 w/w water/37% strength by weighthydrochloric acid. The resulting precipitate was filtered off, washedwith water, dried and subsequently chromatographed over silica gel(column 12×120 cm) with toluene, the product being eluted as the first,orange-colored fraction.

Recrystallization from methylene chloride/methanol gave 6.3 g ofN-(2,6-diisopropylphenyl)-1,6-di(4-tert-butylphenoxy)-9-bromoperylene-3,4-dicarbimideas a red solid of melting point 297° C., which corresponds to a yield of33%.

Examples Ib' to 4b'

The method of Example 1b was also employed to prepare the perylimidesIIb' mentioned in Table B by reacting the correspondingtribromoperylimides IIIa' with phenols

                  TABLE B                                                         ______________________________________                                                                    Yield        mp.                                  Ex.  R           Ar         in %  Color  [° C.]                        ______________________________________                                        1b   2,6-Diisopropyl-                                                                          4-tert-Butyl-                                                                            33    red    297                                       phenyl      phenyl                                                        1b' 2,6-Diisopropyl-                                                                          Phenyl     42    red    >300                                      phenyl                                                                   2b   Dodecyl     4-tert-Butyl-                                                                            33    reddish                                                                              >300                                                  phenyl           orange                                      3b   4-tert-Butyl-                                                                             4-tert-Butyl-                                                                            16    red    >300                                      phenyl      phenyl                                                        3b' 4-tert-Butyl-                                                                             Phenyl     26    red    >300                                      phenyl                                                                   ______________________________________                                    

B2) Preparation of novel 1,7-diaryloxy-9-bromoperylene-3,4-dicarbimidesof the formula IIIb' ##STR15##

Example 6b

R=2,6-diisopropylphenyl; Ar=4-tert-butylphenyl

The method of Example 1b was employed to react the tribromoperylimide ofExample 6a with 4-tert-butylphenol.

This gave 7.4 g ofN-(2,6-diisopropylphenyl)-1,7-di(4-tert-butylphenoxy)-9-bromoperylene-3,4-dicarbimideas a red solid of melting point 289° C., which corresponds to a yield of39%.

C1) Preparation of1,1',6,6'-tetraaryloxy-3,3',4,4'-biperylenetetracarboxylic diimides IV'##STR16##

Example 1c

mixture of 385 mg (1.4 mmol) of bis(1,5-cyclooctadiene)nickel, 126 mg(1.17 mmol) of 1,5-cyclooctadiene and 185 mg (1.17 mmol) of2,2'-bipyridyl in 60 ml of N,N-dimethylformamide was stirred in a 100 mlSchlenk flask at room temperature under argon for 1 h, admixed with 2 g(2.33 mmol) of the bromoperylimide of Example 1b and then stirred at 70°C. for 2 d.

The workup was carried out similarly to Example 1b, except that only 1 lof the water-hydrochloric acid mixture was used and therecrystallization was carried out from methylene chloride.

This gave 1.55 g ofN,N'-bis(2,6-diisopropylphenyl)-1,1',6,6'-tetra(4-tert-butylphenoxy)-3,3',4,4'-biperylenetetracarboxylicdiimide as a red powder of melting point 259° C., which corresponds to ayield of 86%.

Examples 1c' to 3c'

The method of Example 1c was also employed to prepare the piperylenesIV' mentioned in Table C by coupling the bromoperylimides IIIb'.

                  TABLE C                                                         ______________________________________                                                                    Yield        mp.                                  Ex.    R          Ar        in %   Color [° C.]                        ______________________________________                                        1c     2,6-Diiso- 4-tert-Butyl-                                                                           86     red   259                                         propylphenyl                                                                             phenyl                                                       1c'   2,6-Diiso- Phenyl    88     red   >300                                        propylphenyl                                                           2c     Dodecyl    4-tert-Butyl-                                                                           79     reddish                                                                             >300                                                   phenyl           brown                                      3c     4-tert-Butyl-                                                                            4-tert-Butyl-                                                                           64     reddish                                                                             >300                                        phenyl     phenyl           brown                                       3c'   4-tert-Butyl-                                                                            Phenyl    65     reddish                                                                             >300                                        phenyl                      brown                                      ______________________________________                                    

C2) Preparation of1,1',7,7'-tetraaroxy-3,3',4,4'-biperylenetetracarbimides IV" ##STR17##

Example 6c

R=2,6-diisopropylphenyl; Ar=4-tert-butylphenyl

The method of Example 1c was followed to couple the bromoperylimide ofExample 6b.

This gave 1.37 g ofN,N'-bis(2,6-diisopropylphenyl)-1,1',7,7'-tetra(4-tert-butylphenoxy)-3,3'-4,4'-biperylenetetracarboxylicdiimide as a red powder of melting point 273° C., which corresponds to ayield of 76%.

D1) Preparation of novel1,6,11,16-tetraaryloxyquaterrylene-3,4:13,14-tetracarboxylic diimides I'##STR18##

Example 1d

A mixture of 80 g of pulverized potassium hydroxide, 80 ml of ethanol, 6g of glucose and 500 mg (0.32 mmol) of the biperylene derivative ofExample 1c was heated at 120° C. under argon for 2.5 h.

After cooling down to room temperature, the reaction mixture was addedto 420 ml of water and admixed with 80 ml of concentrated hydrochloricacid. The resulting precipitate was filtered off and washed successivelywith saturated aqueous potassium carbonate solution, water, methanol anddiethyl ether. The soluble by-products were removed by additionalextraction with chloroform.

This gave 421 mg ofN,N'-bis(2,6-diisopropylphenyl)-1,6,11,16-tetra(4-tert-butylphenoxy)quaterrylene-3,4:13,14-tetracarboxylicdiimide as a green powder of melting point >300° C., which correspondsto a yield of 85%.

These are some analytical data for this quaterrylimide:

¹ H-NMR (500 MHz, CDCl₃): δ=9.09 (d,4H), 8.32 (s,4H), 7.76 (d,4H), 7.41(t,2H), 7.34 (d,8H), 7.28 (d,4H), 7.00 (d,8H), 2.76 (m,4H), 1.26(s,36H), 1.13 (d,24H) ppm;

¹³ C-NMR (125,5 MHz, CDCl₃): δ=163.0, 153.6, 152.9, 147.0, 145.8, 131.2,130.9, 130.8, 129.4, 129.2, 128.9, 127.7, 127.5, 127.2, 126.4, 125.2,124.3, 123.9, 122.5, 121.6, 117.4, 34.4, 31.4, 29.2, 24.1 ppm;

IR (KBr): ν=1707 (s,C═O), 1669 (s,C═O) cm⁻¹ ;

UV/VIS (CH₂ Cl₂): λ_(max) (ε)=262 (95819), 271 (97645), 382 (12895), 709(71931), 781 (166571) nm;

Fluorescence (CH₂ Cl₂): λ_(max) =806 nm.

Of particular importance for the use as fluorescent dye is thesolubility of the quaterrylimide in organic solvents: 25-30 mg/ml ofchloroform at room temperature, 80 mg/ml of tetrachloroethane at 135° C.

By comparison, the unsubstituted N,N'-dodecylquaterrylimide known fromEP-A-596 292 is insoluble in both solvents and the analogous,unsubstituted N,N'-bis(2,6-diisopropylphenyl)quaterrylimide almostinsoluble (solubility <0.2 mg/ml of chloroform, 1-2 mg/ml oftetrachloroethane).

Also of interest is the bathochromic shift of the longest-wavelengthabsorption band by 20 nm in the UV/VIS spectrum, compared with thecorresponding unsubstituted quaterrylimide.

D2) Preparation of novel1,7,10,16-tetraaryloxyquaterrylene-3,4:13,14-tetracarboxylic diimides I"##STR19##

Example 6d

R=2,6-diisopropylphenyl; Ar=4-tert-butylphenyl

The method of Example 1d was followed to oxidize the biperylene ifExample 6c.

This gave 318 mgN,N'-bis(2,6-diisopropylphenyl)-1,7,10,16-tetra(4-tert-butylphenoxy)quaterrylene-3,4:13,14-tetracarboxylicdiimide as a bluish green powder of melting point >300° C., whichcorresponds to a yield of 64%.

D3) Preparation ofN,N-bis(2,6-diisopropylphenyl)-1,7,9,11,17,19-hexabromoquaterrylene-3,4:13,14-tetracarboxylicdiimide I'" ##STR20##

Example 7

1.0 g of unsubstituted N,N'-bis(2,6-diisopropylphenyl)quaterrylimide,obtained by bromination of unsubstitutedN-2,6-diisopropylperylene-3,4-dicarbimide to the 9-bromoperylimidesimilarly to Example 6a, subsequently coupling similarly to Example 1cand oxidation similarly to Example 1d, was brominated similarly toExample 1a except for the doubling of the reaction time to 12 h.

This gave 1.3 g of I'" as a dark red solid having a purity of 85% (15%of tetrabromo product) and a melting point >300° C., which correspondsto a yield of 91%.

We claim:
 1. Quaterrylenetetracarboxylic diimides of formula I: ##STR21## wherein R is hydrogen;C₁ -C₃₀ -alkyl whose carbon chain optionally is interrupted by one or more of --O--, --S--, --NR¹ --, --CO-- and/or --SO₂ -- and which optionally is monosubstituted or polysubstituted by cyano, C₁ -C₆ -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which optionally contains additional heteroatoms and optionally is aromatic, where R¹ is hydrogen or C₁ -C₆ -alkyl; C₅ -C₈ -cycloalkyl whose carbon skeleton optionally is interrupted by one or more of --O--, --S-- and/or --NR¹ --; aryl or hetaryl, each of which optionally is monosubstituted or polysubstituted by C₁ -C₁₈ -alkyl, C₁ -C₆ -alkoxy, cyano, --CONHR², --NHCOR² and/or aryl- or hetaryl-azo, each of which optionally is substituted by C₁ -C₁₀ -alkyl, C₁ -C₆ -alkoxy or halogen, where R² is hydrogen; C₁ -C₁₈ -alkyl; aryl or hetaryl, each of which optionally is substituted by C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen or cyano; X is halogen; C₁ -C₁₈ -alkyl; aryloxy, arylthio, hetaryloxy or hetarylthio, each of which optionally is substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; n is from 2 to
 12. 2. Quaterrylenetetracarboxylic diimides as claimed in claim 1, wherein:R is C₈ -C₂₀ -alkyl whose carbon chain optionally is interrupted by one or more of --O-- or --S-- and which optionally is monosubstituted or polysubstituted by C₁ -C₄ -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which optionally contains additional heteroatoms and optionally is aromatic;C₅ -C₈ -cycloalkyl; phenyl or hetaryl, each of which optionally is monosubstituted or polysubstituted by C₁ -C₁₂ -alkyl, C₁ -C₄ -alkoxy, --CONHR² and/or --NHCOR² and/or monosubstituted by aryl- or hetaryl-azo, each of which optionally is substituted by C₁ -C₁₀ -alkyl, C₁ -C₆ -alkoxy, halogen or cyano; X is halogen; phenoxy, phenylthio, pyridyloxy, pyridylthio, pyrimidyloxy or pyrimidylthio, each of which optionally is subtituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; n is from 2to
 8. 3. Quaterrylenetetracarboxylic diimides as claimed in claim 1, wherein:R is C₈ -C₂₀ -alkyl whose carbon chain optionally is interrupted by one or more of --O-- and optionally is substituted by C₁ -C₄ -alkoxy;C₅ -C₈ -cycloalkyl; phenyl, pyridyl or pyrimidyl, each of which optionally is monosubstituted or polysubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, --CONHR² or --NHCOR² and/or monosubstituted by phenylazo or naphthylazo, each of which optionally is substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or cyano, where R² is C₁ -C₄ -alkyl or phenyl each of which optionally is substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; X is halogen; phenoxy, phenylthio, pyrimidyloxy or pyrimidylthio, each of which optionally is substituted by C₁ -C₄ -alkyl; n is from 2to
 8. 4. A process for preparing quaterrylenetetracarboxylic diimides of formula Ia: ##STR22## wherein: R is hydrogen;C₁ -C₃₀ -alkyl whose carbon chain optionally is interrupted by one or more of --O--, --S--, --NR¹ --, --CO-- and/or --SO₂ -- and which optionally is monosubstituted or polysubstituted by cyano, C₁ -C₆ -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which optionally contains additional heteroatoms and optionally is aromatic, where R¹ is hydrogen or C₁ -C₆ -alkyl; C₅ -C₈ -cycloalkyl whose carbon skeleton optionally is interrupted by one or more of --O--, --S-- and/or --NR¹ --; aryl or hetaryl, each of which optionally is monosubstituted or polysubstituted by C₁ -C₁₈ -alkyl, C₁ -C₆ -alkoxy, cyano, --CONHR², --NHCOR² and/or aryl- or hetaryl-azo, each of which optionally is substituted by C₁ -C₁₀ -alkyl, C₁ -C₆ -alkoxy or halogen, where R² is hydrogen; C₁ -C₁₈ -alkyl; aryl or hetaryl, each of which optionally is substituted by C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen or cyano; X is halogen; C₁ -C₁₈ -alkyl; aryloxy, arylthio, hetaryloxy or hetarylthio, each of which optionally is substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; p is from 4to 8,which comprises a) reacting perylene-3,4-dicarbimides of formula Ia ##STR23## where q is from 2 to 4, with elemental bromine in the presence of an inert diluent at from 40 to 50° C. to form brominated perylimides of formula IIIa: ##STR24## b) coupling the brominated perylimides IIIa in the presence of an organic metal complex as catalyst, free ligand molecules and an inert diluent to form biperylene derivatives of formula IVa: ##STR25## and c) converting the biperylene derivatives IVa by heating in the presence of an oxidizing agent and of an alkaline reaction medium into the quaterrylenetetracarboxylic diimides Ia.
 5. A process for preparing quaterrylenetetracarboxylic diimides of formula Ib: ##STR26## wherein: R is hydrogen;C₁ -C₃₀ -alkyl whose carbon chain optionally is interrupted by one or more of --O--, --S--, --NR¹ --, --CO-- and/or --SO₂ -- and which optionally is monosubstituted or polysubstituted by cyano, C₁ -C₆ -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which optionally contains additional heteroatoms and optionally is aromatic, where R¹ is hydrogen or C₁ -C₆ -alkyl; C₅ -C₈ -cycloalkyl whose carbon skeleton optionally is interrupted by one or more of --O--, --S-- and/or --NR¹ --; aryl or hetaryl, each of which optionally is monosubstituted or polysubstituted by C₁ -C₁₈ -alkyl, C₁ -C₆ -alkoxy, cyano, --CONHR², --NHCOR² and/or aryl- or hetaryl-azo, each of which optionally is substituted by C₁ -C₁₀ -alkyl, C₁ -C₆ -alkoxy or halogen, where R² is hydrogen; C₁ -C₁₈ -alkyl; aryl or hetaryl, each of which optionally is substituted by C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen or cyano; Hal is chlorine or bromine; p is from 4 to 8,which comprises a) reacting perylene-3,4-dicarbimides of formula IIb: ##STR27## with elemental halogen in the presence of an inert diluent at from 60 to 140° C. to form halogenated perylimides of formula IIIb: ##STR28## where Hal is bromine or chlorine and q is from 2 to 4, b) coupling the halogenated perylimides IIIb in the presence of an organic metal complex as catalyst, free ligand molecules and an inert diluent to form biperylene derivatives of formula IVb: ##STR29## and c) converting the biperylene derivatives IVb by heating in the presence of an oxidizing agent and of an alkaline reaction medium into quaterrylenetetracarboxylic diimides Ib.
 6. A process for preparing quaterrylenetetracarboxylic diimides of the formula Ic ##STR30## where: R is hydrogen;C₁ -C₃₀ -alkyl whose carbon chain optionally is interrupted by one or more of --O--, --S--, --NR¹ --, --CO-- and/or --SO₂ -- and which optionally is monosubstituted or polysubstituted by cyano, C₁ -C₆ -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which optionally contains additional heteroatoms and optionally is aromatic, where R is hydrogen or C₁ -C₆ -alkyl; C₅ -C₈ -cycloalkyl whose carbon skeleton optionally is interrupted by one or more of --O--, --S-- and/or --NR¹ ; aryl or hetaryl, each of which optionally is monosubstituted or polysubstituted by C₁ -C₁₈ -alkyl, C₁ -C₆ -alkoxy, cyano, --CONHR², --NHCOR² and/or aryl- or hetaryl-azo, each of which optionally is substituted by C₁ -C₁₀ -alkyl, C₁ -C₆ -alkoxy or halogen, wherein R² is hydrogen; C₁ -C₁₈ -alkyl; aryl or hetaryl, each of which optionally is substituted by C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen or cyano; Z is aryloxy, arylthio, hetaryloxy or hetarylthio, each of which optionally is substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; p is from 4 to 8,which comprises a) reacting perylene-3,4-dicarbimides of formula IIb ##STR31## with elemental halogen in the presence of an inert diluent at from 60 to 140° C. to form halogenated perylimides of formula IIIb;where Hal is bromine or chlorine and q is from 2 to 4, ##STR32## a') converting the halogenated perylimides IIIb in the presence of a tertiary nitrogen base as solvent and optionally of an inorganic base with nucleophiles of the formula:

    Z--K

where K is an alkali metal cation or hydrogen, into substituted perylimides of formula IIIc: ##STR33## b) coupling the substituted perylimides IIIc in the presence of an organic metal complex as catalyst, free ligand molecules and an inert diluent to form biperylene derivatives of formula IVc: ##STR34## and c) converting the biperylene derivatives IVc by heating in the presence of an oxidizing agent and of an alkaline reaction medium into the quaterrylenetetracarboxylic diimides Ic.
 7. A process for preparing quaterrylenetetracarboxylic diimides of formula Id: ##STR35## where: R is hydrogen;C₁ -C₃₀ -alkyl whose carbon chain optionally is interrupted by one or more of --O--, --S--, --NR¹ --, --CO-- and/or --SO₂ -- and which optionally is monosubstituted or polysubstituted by cyano, C₁ -C₆ -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which optionally contains additional heteroatoms and optionally is aromatic, where R¹ is hydrogen or C₁ -C₆ -alkyl; C₅ -C₈ -cycloalkyl whose carbon skeleton optionally is interrupted by one or more of --O--, --S-- and/or --NR¹ --; aryl or hetaryl, each of which optionally is monosubstituted or polysubstituted by C₁ -C₁₈ -alkyl, C₁ -C₆ -alkoxy, cyano, --CONHR², --NHCOR² and/or aryl- or hetaryl-azo, each of which optionally is substituted by C₁ -C₁₀ -alkyl, C₁ -C₆ -alkoxy or halogen, wherein R² is hydrogen; C₁ -C₁₈ -alkyl; aryl or hetaryl, each of which optionally is substituted by C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen or cyano; Y is halogen; aryloxy, arylthio, hetaryloxy or hetarylthio, each of which optionally is substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; n is from 2to 12,which comprises a) reacting perylene-3,4-dicarbimides of formula IIb: ##STR36## with elemental bromine in the presence of an inert diluent at from 40 to 50° C. to form brominated perylimides of formula IIId: ##STR37## b) coupling the brominated perylimides IIId in the presence of an organic metal complex as catalyst, free ligand molecules and an inert diluent to form biperylene derivatives of formula IVd; ##STR38## c) converting the biperylene derivatives IVd by heating in the presence of an oxidizing agent and of an alkaline reaction medium into unsubstituted quaterrylenetetracarboxylic diimides Id' ##STR39## d) reacting the unsubstituted quaterrylenetetracarboxylic diimides Id' with elemental halogen in the presence of an inert diluent at from 60 to 140° C. to form the halogenated quaterrylenetetracarboxylic diimides Id (Y:Hal), and optionally e) converting the halogenated quaterrylenetetracarboxylic diimides by reaction with nucleophiles of the formula:

    Z--K

where Z is aryloxy, arylthio, hetaryloxy or hetarylthio, each of which optionally is substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, and K is an alkali metal cation or hydrogen, in the presence of an inorganic base and of a tertiary nitrogen base into the quaterrylenetetracarboxylic diimide of formula Id where Y is Z.
 8. A fluorescent dye or pigment comprising quaterrylenetetracarboxylic diimides of formula I as claimed in claim
 1. 9. Quaterrylenetetracarboxylic diimides of formula I: ##STR40## where R is hydrogen;C₁ -C₃₀ -alkyl whose carbon chain optionally is interrupted by one or more of --O--, or, --NR¹ --, and which optionally is monosubstituted or polysubstituted by cyano, C₁ -C₆ -alkoxy or a 5-, 6- or 7-membered heterocyclic radical which is attached via a nitrogen atom and which optionally contains additional heteroatoms and optionally is aromatic, where R¹ is hydrogen or C₁ -C₆ -alkyl; C₅ -C₈ -cycloalkyl; aryl or hetaryl, each of which optionally is monosubstituted or polysubstituted by C₁ -C₁₈ -alkyl, C₁ -C₆ -alkoxy, cyano, --CONHR², --NHCOR² and/or aryl-azo, each of which optionally is substituted by C₁ -C₁₀ -alkyl, C₁ -C₆ -alkoxy or halogen, where R² is hydrogen; C₁ -C₁₈ -alkyl; aryl, which optionally is substituted by C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen or cyano; X is halogen; C₁ -C₁₈ -alkyl; aryloxy, arylthio, hetaryloxy or hetarylthio, each of which optionally is substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; n is from 2 to
 8. 